Water-soluble reactive xanthene dyestuffs and process for preparing them

ABSTRACT

Novel water-soluble, reactive xanthene dystuffs of the   IN WHICH R1 and R2, being identical or different, each represent hydrogen, chlorine, bromine, lower alkyl or lower alkoxy, X represents oxygen, sulfur or   AND M REPRESENTS A NUMBER FROM 1 TO 3, SAID DYSTUFFS BEING HIGHLY SUITABLE FOR THE DYEING OR PRINTING OF LEATHER, WOOL, SILK, POLYAMIDE OR POLYURETHANE FIBRES, ESPECIALLY OF CELLULOSE FIBRES, THE DYEINGS OR PRINTS OBTAINED ON CELLULOSE FIBRES WITH THE SAID DYESTUFFS BEING IN PART DISTINGUISHED BY HIGH BRILLIANCY AND GOOD FASTNESS PROPERTIES, PARTICULARLY BY GOOD FASTNESS TO WET PROCESSING.

United States Patent m1 Meininger et ttl.

WATER-SOLUBLE REACTIVE XANTHENE DYESTUFFS AND PROCESS FOR PREPARING THEMInventors: Fritz Melninger. Frankfurt am Main. Follter Koltlhas.lfielkheim.

Taunus. both of Germany Auignee: lloeelist Mttiengeseliseiuit.

Frankfurt am Main. Germany Filed: June 30. 1972 Appl. No.: 267.958

Foreign Application Priority Data July 2. I97! Germany 2l32963 U.S. Cl.260/28l: 260/240.l: 260/239.ll; 260/249; 260/2495; 260/250 A; 260/2565SA. 260/287 R. 260/288 R; 260/289 R; 8H2. 8/542; 8/37. 8/63; 8/!62 Rllll 3,888,862

| l June 10, 1975 [51] Int. Cl. C07d 35/00 [58] Field oi Search 260/281Primary Examiner-J. A. Narcuvage Attorney. Agent. or Firm-Curtis. Morris84 Stafford Novel water-soluble. reactive xunthcne dyestulT for thedyeing or printing of leather. wool. ailk. polyamide. polyurethane orcellulose fibers.

ABSTRACT 6 Claims. No Drawings l WATER-SOLUBLE Rl-IAL'TlVl-lXAYl'lll-ZNE DYI-LsTlFFS AND IRfXlZSS FOR PREPARING THEM The presentinvention relates to nets reactive santhene dyestulTs of the generalforntula t l l alkyl chain. X represents an oxygen or sulfur atom or a(O-group. or is a nuntber from I4. and R, is a group of the generalformula (2t in which W represents a bivalent bridge member such as. forexample. the groups --CH,-CH,-and CH ,-CH,-CH,. A represents a bivalent.monoor binuclear aromatic group. for example a phenylene or naphthylenegroup or a bivalent diphenyl. diphenyl ether. diphenyiamine. diphenylsulfide or diphenyl sulfone group. in which the group A in the aromaticnuclei may be substituted by halogen atoms. preferably chlorine orbromine atoms. lower alkyl. lower alkoxy. hydroxyl. carbosyl. sulfo ornitro groups. 8 represents a bivalent bridge member such as -CH,. CH-,-('H,-or -NR.. R. being a hydrogen atom or an optionally substitutedlower alkyl group. preferably a methyl. ethyl. fl-hydrosyethyl orfi-sulfoethyl group. Y represents a reactive group. and n. p and q standfor 0 or I and r stands for l or 2.

Under reactive groups Y. there are to be understood those which containone or several reactive groups or substituents that can be split-off andwhich. upon application of the dyestuffs on cellulose materials in thepresence of acid-binding agents and optionally under the action of heat.react with the hydroxyl groups of cellulose while forming covalent bondsor upon application on super-polyamide fibers such as wool. react withthe NH group of these fibers. A great number of such fibre-reactivegroupings is known from literature.

Reactive groups which are suitable according to the intention and whichcontain at least one such substituent. which is capable of beingsplit-oft and which is bound to a heterocyclic or aliphatic group. areamong others those which contain at least one reactive substituent boundto a S- or h-mentbered heterocyclic ring. such as the monoazine.diazine. triazine ring. for example. a pyridine. pyrimidine. pyridazine.pyraline. thiatine. marine or an asymmetrical or symmetrical trialinering or to such a ring system which contains one or several annellatedaromatic rings such as a quinoline. phthalazine. cinnoline. qulnoamline.quinoxaline. acridine. phenazine and phenanthridine ring system;accordingly. the 5- or h-membered hcterocyclic rings which contain atleast one reactive substituent are prefsuch 2 crably those which containone or several nitrogen atoms. and 5- or. preferably. b-mentbcredannellatetl carboxylic rings. Among the reactive substituents of theheteroeycle. there may be mentioned. for example halogen ((l. llr of Ft.ammonium. including hydrant ium. sulfonium. sulfonyl. azido (Nrhodanido. thio. thio-ether. oxy-ether. sullinic acid and sulfonic acid.In particular there may be mentioned. for exantplc chloroand3.6-dichloro-LI-diazinyl groups. month or dihalogeno symmetricaltriazinyl groups. for example 2.4-dichlorotriazinyl-b.2-amino-4-chlorotriaziny!-o. 2-alkylantino-4-ehlorotriazinyl-b. such asI mcthylamino-4-chlorotriazinyl-b. Z-ethylaminoor 2propylamino-4-chlorotriazinyl-b. 2-l3-oxetltylamino-4-chlorotriazinyl-b. Z-di-B-oxethylamino-4- chlorotriazinyl-o and thecorresponding sulfuric acid semi-esters.2-diethylamino-4-chlorotriazinyl-b. Z- morpholinoorZ-pipcridino-J-chlorotriazinyl-b. 2-cyclohcxylamino-J-chlorotriazinyl-b. \l-aminoand substitutedarylamino-J-ehlorotriazinyl-o, znch asZ-phenylamino-4-chlorotriazinyl-b-. 2-(o-. mor ,t carboxyorsulfophenyll-amino-4-ehlorotriazinyl-o.

2-alltosy--l-chlorotriazinyl-b cthoxy-J-chlorotriazinyl-b.

tphenylsulfonylmethoxy )-4-Cltlttlttll'l;tlln)'|-b aryloxy andsubstituted arylosy-4-chlorotriazinyl-h.

as 2-phenoxy-4-chlorotriazinyl-b. l-lpsulfophenyli-oxyA-chlorotriazinyl-b. 240-. m or pmethylor-melltoxyphertyll-oxy-4-chlorotriazinylh.

such as Z-mcthoxyorz-alkylmercaptoor Z-arylmercaptoor Ltsuhstituted aryli-mercapto-J-chlorotriazinyl-h. such as 2-13- hydroxyethyli-mercapto-4-chlorotriazinyl-b. 2 pbenyImercapto-J-ehIorotriazinyl-o. 24

methylphenyl l-mercapto-J-chlorotriazinyl-o. 24 4methylphenylt-mercapto-4-chlorotriazinyl-b. 2-(2tlinitro)-phenylmercaptoA-chlorotriazinyl-o.

2-mcthyl-l-chlorotriazinyl-f 2-phenyl-4 chlorotriazinyl-b. mono-. diortrihalogenopyrimidinyl groups. such as 2.4-dichloropyrimidinyl-b. 2.4.5-trichloropyrimidinyl-b. 2.4-dichloro-S-nitroor -5- methylor-5-carbosymethylor -S-earboxyor -5- cyanoor -5-vinyl or -5-sulfoor-$-mono-. -dior -tri chloromethylor -5-carlxi-alkoxy-pyrimidinyl-b. 2.0-

dichloropyrimidinc-4-carbonyl. 2 .4 dichloropyrimidine-S-carbonyl.2-ehloro-4- methylpyrimidine-S-carbonyl. Z-methy l--tchloropyrimidine-S-carbonyl. fluoropyrimidine-S-carbonyl.dichloropyrimidine-S-carbonyl. 2 .4 J trichloropyrimidine-5-ca rbonyl. 2.4- dichloropyrimidine-S-sulfonyl. l-chlon uinosaline-I- carbonyl. 2 orJ-monochloroquinoxaline-b-earbonyI.

Z-methyIthio-J- b-methyl-l-L 2- or .l-monoehloroquinoxaline-b-sulfonyl.2.3 diehloroquinoxaline-b-carbonyl. 2 .3-dichloroquinoxaline-b-sulfonyl. l .4- tlichlorophthalaline-b-sulfonyl or-b-carbonyl. 2 .4

dichlorts uinazoline-7-or -b-sulfonyl or -carbon vl. 2- or 3 or4-t4'.S'-dichloropyridazone-b'-yll phenylsulfonyl or -carbonyl.1H4.$-dichloropuridazone-G-rl-l l-ethylcarbonyl N-methyl-N -t 2 .4-dichlorotriazinyl-bt-car amyl. N-methyl-N't 2-methylaminod-chlorotriazinyl-bi-carbamyl. N methyl-N42-dimethylaminw-t-chlorotriazinyl-r\- lwith the amines of the formula(4) or (5). R R W. A. B. Y. n. p. q and r having the meanings givenabove. at a molar ratio of H or with an excess quantity of an amine ofthe formula (4) or (5) apt-[U1 [A L (di au ea es (s) in water or in anorganic solvent such as methanol. ethanol. isopropanol or in anethyleneglycol-monoalltyl ether. dimethylformamide or dimethylsulfoxideas described in German Patent No. l.297.259. by isolation of thereaction products in the usual manner and by treatment of the productswith concentrated or fuming sulfuric acid at room temperature or at anelevated temperature. the degree of sulfuration depending on thetemperature used. the concentration of the sulfuric acid and thereaction time. Suitably. the sulfuration is carried out at temperaturesin the range of from about EDT to about l70'C using 95 percent fumingsulfuric acid with it SO. content of up to about ZO percent.

Another process for preparing the dyestuffs of the general formula lcomprises reacting eompouunds of the formula (6) which are obtained inknown manner from the compounds of the formula (3) or (3a). with aminesof the formula (4) at a molar ratio of hi or with an excess of the amineof the formula (4) in water at elevated temperatures. optionally underpressure.

Further variants of the preparation of the product of the inventioncomprise the reaction of the sulfonic acids of the general formula to)with the amines (a) of the formula (7).

(b) of the formula (8) M lk [v 1 ]p or (c) of the formula il ll- [ii 1[A L [(m -tzo -ctt -ctt -on 1r (5 in which W. A. 8. n. p. q and r havethe meanings giten above and R. stands for an acyl group. for examplethe acetyl group. at a molar ratio of l:l or with an XCcss of amines ofthe formula (7 t. (8) or (5). in water at an elevated temperature.optionally in the presence of a condensing agent such as sodium acetateand optionally under pressure. The compounds obtained in the case (a)are then transformed by reduction according to ltnown processes intocompounds of the formula (l0) and the compounds obtained in the case (b)are likewise transformed by hydrolysis in known manner into compounds ofthe formula H0). The compounds obtained according to method (c)correspond to the formula (l l [A L [(rQ -se -crt wa m] The dyestuffs ofthe invention corresponding to the formula l are prepared from theintermediate products of the formula ID) by condensation with a reactivecomponent of the general formula l2) III in which Z represents asubstituent that may he split-off and Y stands for reactive groups ofthe meaning given above.

Reactive components of the formula l2) which are suitable for the abovepurpose are. for example. those on which the aforementioned reactivegroups Y are based. i.e.. in general the halides and in particular thechlorides of the acyl components Y. Front the great pyridazone-t l;further heterocyclic reactive components vvith mobile halogen are amongothers I- or 3- monoehloroquinimiline-b-carbovylic acid chloride or-b-sulfonic acid chloride. L or 3- monobriimoquinovaline-b-carbosylieacid bromide or -b sulfonie acidbroniidc.'..3-dichliirmplinosalinc-bcarbosylic acid chloride or-b-sulfonic acid chloride. 2.3-dibromoquinosaline-b-carbosylic acidbromide or -(s-sulfonic acid bromide.l.4-dichIorophthalazine-hcarboxylic acid chloride or -b-sulfonic acidchloride and the corresponding bromine compounds. 2.4-dichloroquinazoline-bor -7-carbovylic acid chloride or -sulfonic acidchloride and the corresponding bromine compounds. 2- or 3- or 4-H. 5'-dichloropyridazone-b'-yl-l l-phenylsulfonic acid chloride orcarbosylicacid chloride and the corresponding bromine compounds.fi-t4'.5'-dichloropyridazone-(i'- yll l-ethylearlmsylic acid chloride.2- chlorm uinoxaline-S-carboxylie acid chloride and the correspondingbromine compounds. N-methyl-N-t 2.4- dichlorotriazinyl-bl-carbamidicacid chloride. N- methyl-N -i Z-chlorod-methylaminotriazinyl-blcarbamidie acid chloride. N-methyl-N-l2-chloro-4-dimethylamino-triazinyl-bi-carbamidic acid chloride. .\-methyloraminoacctyl chloride. N-mcthyl-. N-cthylor N- hydrovyethyLN-t2.3-dichloroquinoxaline-b-sulfonylor -b-carbonyll-aminoacetyl chlorideand the corresponding bromine derivatives. further 2-chlorobirnzthiazole-$- or -b-carboxylic acid chloride or or -b-sulfonicacid chloride and the corresponding brontine compounds. 2-arylsulfonylorZ-allvylsulfunylbcnzthiazole-S- or -6-carboxylic acid -5- or -6-sulfonicacid chloride. such as 2-methylsulfonylor l-ethylsulfonylorZ-phenylsulfonyl-bcnzthialolc-fior -6- sulfonic acid chloride or or-h-carboxylic acid chloride as well as the correspondingsulfonylbenzthiamle derivatives containing sulfonic acid groups in theannellatcd benzene ring. 3.5-bismethylsulfonyl-isothiazole-J-carboxylicacid chloride. 2-chlorobenzosazole-S- or -b-carbovylic acid chloride or-sulfonic acid chloride as well as the correspondig bromine derivatives.I-chlorobenzimidazole-5- or -6- carboxylic acid chloride or -sull'onicacid chloride as well as the corresponding bromine derivatives. 2-chlorol -methylbenzimidazole-5- or -b-carboxylic acid chloride or-sulfonic acid chloride as well as the corresponding brominederivatives. 2-chloro-4- ntethylthiazolc-t l.3l-$-carhoxylie acidchloride or -4- or -5-sulfonic acid chloride. 2-chlorothiazole--lor -5-sulfonic acid chloride and the corresponding bromine derivatives.

Front the series of aliphatic reactive components. there may bementioned. for esample: acrylic acid chloride. mono-. diortrichloro-acrylic acid chloride. -chIoropropionic acid chloride.3-phenylsulfonylpropionic acid chloride. 3- methylsulfonyl-propionicacid chloride. -ethylsulfonyl-propionic acid chloride.-

3-ehIonrethane-sulfochloridc. chloromethane sulfochloride.Z-chloroacetyl chloride. 2.2.3.3- tctrafluorocyclobutanel -carbo\ylicacid chloride.

[342.2.3.3-tctralluorocyclobutyl-ll-acrylic acid chloride.[342.3.Mrifluoro-Z-chlorocyclobutanc-l l-carboxylic acid chloride.B-methylsulfonyl acrylic acid chloride. u-mcthylsulfonyl-acrylic acidchloride. n-bromoacrylic acid chloride.B-bromoacrylic acidN-ethyl-N-lZA-dichlorotrialinyl-blchloride andB-chloroethylsnlfonyl-chlorocarlwnyl 2.2.l l-cycloheptane Thesecondensation reactions are carried out. in general. in an aqueous.organic or aqueous-organic me dium in the weakly alkaline. neutral orvveakly acid range.

The dyestuffs ol'the formula l l )ofthe present inven tion are obtainedfrom the intermediate product of the formula l l l by treatment withsull'ating agents. phosphorylating agents. halogenating agents. alkylorarylsulfonic acid halides or -carboxylic acid halides or -carboxylieacid anhydrides. Y standing for the group SO,CH,CH,OSO .H. S(),( ll ,C H,t )l( .l l -SO,CH,CH,-halogen or -S(),(l i:(ll:O-acyl. l'he dyestuffsso-obtained may be converted by treatment with agents having an alkalineaction. for example all kali-mctal hydroxides or alkali-metal carbonatessuch as sodium hydroxide or sodium carbonate. into dyestuffs of thegeneral formula l l l. in which Y stands for thhe grouping SO,CH=(ll,.and the dyestuffs so obtained may be converted by the reaction(addition! with salts of thiosulfuric acid. such as sodium thiosulfate.with dialkyl-amines. such as dimethylor diethy lamine. or with phenol.into dyestuffs of the general formula l l in which Y represents-S0,(ll=(ll,SS(),ll. -S():('H, ClLNtalkyl l, or

Suitable sulfating agents are. for evample. concen trated sulfuric acid.chlorosulfonic acid. amidosulfonic acid. or sulfur-trioxide yieldingcompounds. Suitable pbos'phorylating agents are. for exampleconcentrated phosphoric acid. pyro-. metaor polyphosphoric acid.polyphosphoric acid alkyl esters. phos horovychloride or mixtures ofphosphoric acid and phosphorus-(\' l oxide. As halogenating agents.there may be used. for example thionyl chloride or thionyl bromide.

'l'he xanthene dyestuffs of the formula (1 l obtained according to theprocesses of the invention are isolated by salting out. for example withsodium chloride or otassium chloride. or by spray-drying of the reactionmixture.

The new reactive xanthene dyestuffs of the general formula (I) are verywell suited for the dyeing and printing of various fiber materials. forexample wool. silk. leather. polyamide or polyurethane fibers.especlally however. cellulose-containing fiber materials such as cotton.staple fiber and linen. For this purpose. they may be used according tothe dyeing and printing methods commonly used in the art for reactivedye stuffs and yield on cellulose fiber materials. in the pre ence ofalkaline agents. intense greenish yellow to red dish yellow dyeings andprints which have in part a high brilliancy and good properties offastness. especially good fastness to wet processing.

The following Examples illustrate the invention.

EXAMPLE I I5 Parts by weight of benzothiovanthemdicarboxylicacid-anhydride were stirred in ltltl part by weight of dimethylformamidewith 2| parts by weight of 3-aminophenyl-IS-osethylsulfone and the wholewas boiled for 6 hours under reflux. 'l'he condensation product that hadformed was isolated by dilution to the formula 9 so, ca on, use, it

w as stirred into 400 parts of water. neutralized with so dium acetateand salted out with sodium chloride. After drying and grinding. anorange red powder was obtained which dissolved in water to give areddish yellow solution. Strongly diluted solutions thereof showed agreen fluorescence.

Parts by weight of the dyestul'f soobtained were mixed with 80 parts byweight of urea and dissoivcd in 250 parts by weight of water at aboutBOC. Into this solution. there were stirred at 40'C 400 parts by weightof a neutral alginatc thickener and t5 pans by weight of sodiumcarbonate. This paste was printed on a cotton fabric which was thendried and steamed for ID minutes. soaped and rinsed. A very brilliantreddish yellow print was obtained which showed very good fastness towashing treatments.

EXAMPLE 2 1 mmi M was salted out from the filtrate by means of potassium12 in water to give a reddish. yellow solution. Strongly dilutedsolutions showed a green fluorescence.

A cotton fabric was impregnated with a bath which contained. per liter.g of the dyestuff so-obtained. 3t) g ofsodium sulfate and lb mlof32.5'fi sodium hydrotide solution. reeled onto a skein. wrapped in aplastic foil and allowed to dwell for it hours. After rinsing andsoaping. a very brilliant. reddish yellow dyeing having good propertiesof fastness to wet processin was obtained.

EXAMPLE 3 By reacting 28 parts by weight of the sodium salt ofbcnzoxanthene-carboxylic acid anhydride-sulfonic acid. containing 2.7sulfo groups. in 500 parts by weight of water with it parts by wei ht ofJ- aminophenyl-B-oxethylsulfone in a manner similar to that in Example2. a dyestuff was obtained which. in form of the free acid. correspondedto the formula The aqueous solutions of this dyestuff were greenishyellow and showed a green fluorescence.

On wool. the dyestuff yielded greenish yellow dyeings with highbrilliancy which were fast to washing.

EXAMPLE 4 23 Parts by weight of benzothioxanthenedicarboxylicacid-anhydride-disulfonie acid and ll parts by weight ofl.d-diaminohenzene-Lsulfonic acid were dissolved neutral under additionof sodium hydroxidc solution in 300 parts by weight of water and boiledfor 20 hours under reflux with addition of ill parts by weight ofglacial acetic acid. Then. 20 parts by weight ofB42.2.IiJ-tetrafluoro-4-methyl-cyclobutylllO S A 2 percent dyeing onpolyamide fibers produced in the usual manner in a weakly acetic bathshins-ed. after a treatment with weak alkalis. a bright reddish yellowdyeing having good fastness to washing.

EXAMPLE 5 25 Parts by weight of methoxybenzoxanthenediearboxylicaeid-anhydridedisulfonie acid were condensed in the neutral range atlOO'C in 300 parts by weight of water with 25 parts by weight of3-nitro-anilino--sulfonic acid and the condensation product wassubsequently hydrogenated at a hydrogen pressure of atmospheres gauge inthe presence of IO parts by weight of Raney-nickel. The catalyst wasremoved by filtration and the filtrate was combined with 8 parts byweight of sodium acetate (anhydrous) and 8 parts by weight ofJ-chloro-l.Z-diazine-h-carboxylic acid chloride. and the reaction wascompleted by the slow addition of a solution of sodium carbonate inwater and stirring for several hours; the dyestutl' that had formed wassalted out with sodium chloride. An orange red powder was obtained whichdissolved in water to give a yellow solution which. when stronglydiluted. showed a green fluorescence.

In form ofthe free acid. the dyestutf corresponded to the formula no sgilt-C0 o a O EXAMPLE 6 23 Parts by weight ofbenzothioxanthenediearbosylic acid-anhydr|de-disulfonie acid and I3parts by weight of .1-acctamino-anilino-4-sulfonic acid were dissolvedneutral in 300 parts of water under addition of sodium hydroxidesolution and boiled for 40 hours under reflux. Then. 200 parts by weightof conccntratcd hydrochloric acid were added and the whole was boiledfor 5 hours.

The hydrolysis product. which had been precipitated by means of sodiumchloride. was stirred into 300 parts by weight of water. neutralizedwith sodium hydroxide solution and combined with 5 parts by weight ofsodium bicarbonate and 50 parts by weight of ethylene chloride. Then. lbparts by weight of B-chloroethylehlorocarbonyl-l2.2.l I-cyeloheptanewere added portionwi e. during which time the acid set free wasneutralired with sodium hydroxide solution. After having stirred forsome time. the phases were separated and the dyestuff. which in the formof the free acid corresponded to the formula was salted out withpotassium chloride from the aqueous phase.

The dyestuff. which was obtained in the form of a yellow red powderdissolved in water to give a reddish yellow solution and showed. whendiluted. a green fluorescence. It yielded on cellulose fibers. in thepresence of sodium carbonate. brilliant yellow dyeings and prints havinggood fastncss to wet processing.

EXAMPLE 7 N) Parts by weight of the dyestuff obtained according toExample I were dissolved in It) parts by weight of water and thepH-valuc of this solution was adjusted to l2 by means of sodiumhydroxide solution. After ha ing stirred for a short time at thispH-value. the solution was neutralized with hydrochloric acid and thereaction product was salted out with sodium chloride. The dyestufl.which was obtained in the form of an orange red powder corresponded tothe formula so cmcu fast to washing.

EXAMPLE it its the pH- alue at b by means of percent acetic acid After 5hours the reaction mixture was filtered and the dyestuff of the formulalt dissolved in water to git-e a reddish yellow solution which. whendiluted. showed a green fluorescence. When used for dyeing and printingof cellulose fibers in the absence of agents having alkaline action. butwhen applying an alkaline after-treatment. the dyestufl' yielded reddishyellow dyeings and prints which were and m is a value u! l tn 3.

2. The dycstufl' of the formula 3. The dycstufl' of the fonnula,so,cu,cq oso u 4. The dycstufl' nf thc formula $o,cn cu, cs0,

22 5. The dycstuff of the formula Q so cn cn osogl 6. The dycstufl ofthe formula

1. A WATER-SOLUBLE REACTIVE XANTHENE DYESTUFF OF THE FORMULA
 2. Thedyestuff of the formula
 3. The dyestuff of the formula
 4. The dyestuffof the formula
 5. The dyestuff of the formula
 6. The dyestuff of theformula